High temperature amine-stabilized dcd and/or alkyl thiophosphoric triamide solvent systems and use in agricultural applications

ABSTRACT

An inhibitor composition contains alkyl thiophosphoric triamide (or a mixture of alkyl thiophosphoric triamide and dicyandiamide), dissolved in a liquid medium comprising at least one organic solvent and at least one amine stabilizer, is useful in making fertilizer compositions and in a method of fertilizing target plants.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/205,837 filed Aug. 17, 2015, incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

This invention relates to liquid compositions comprising dicyandiamideand/or an alkyl thiophosphoric triamide, methods for stabilizing suchliquid compositions at high temperatures by incorporating an aminestabilizer, and the use of such compositions.

BACKGROUND OF THE INVENTION

In the agrochemical industry, farmers use various fertilizers to impartmacronutrients to plants either by application to the soil orapplication to plant leaves. Nitrogen, phosphorus, potassium, calcium,magnesium, and sulfur are macronutrients that must be supplied to theplants and soil manually by farmers. In many crops, the amount ofnitrogen supplied is critical to the overall quality and growth of thecrop. Nitrogen is typically supplied in the form of nitrogenous, i.e.,nitrogen precursor-containing, fertilizer compounds, such as urea,ammonium nitrate, or ammonium phosphate fertilizer compounds. Due to thehigh water solubility of these salts, however, applied nitrogen valuesmay be lost due to run-off and leaching of the nitrogenous fertilizercompounds. Once applied, the nitrogenous fertilizer compounds aretypically degraded, for example, by microorganisms present in the soil,to nitrogenous species such as NH₄ ⁺, NO₂ ⁻, NO₃ ⁻, and ammonia gas,that may be even more readily lost through evaporation, run-off, andleaching than the fertilizer compounds themselves. If degradation of thefertilizer compounds occurs at a rate that is faster than thenitrogenous degradation products can be used by the plants, then thenitrogen values in the degradation products are at increased risk ofbeing lost.

Nitrification and/or urease inhibitors are of potential use in delayingdegradation of fertilizer compounds and thereby reducing losses ofnitrogenous degradation products that would otherwise occurred in theabsence of the inhibitors. The use of nitrification and/or ureaseinhibitors in combination with nitrogenous fertilizer compounds tends toincrease the amount of time the nitrogen source remains in the soil andavailable for absorption by the plants, which tends to increase theeffectiveness of the fertilizer and positively impact crop yield andquality.

Aqueous end use fertilizer solutions are typically prepared in the fieldby diluting commercially available concentrated fertilizer compositionswith water. Commonly used concentrated fertilizer compositions includeconcentrated ammonium nitrate compositions, such as, for example, UAN18, UAN 28, UAN 30 and UAN 32.

Dicyandiamide is potentially useful as a nitrification inhibitor in suchaqueous end use fertilizer compositions, but has very low solubility(about 41 grams per liter (“g/l”)) in water and so is difficult toincorporate into the aqueous end use fertilizer compositions,particularly under field conditions

SUMMARY OF THE INVENTION

Urease inhibitors can be used with a fertilizer (i.e., incorporated intoa urea-containing fertilizer, e.g., urea and urea ammonium nitrate(UAN)) to slow the conversion of ammonium to ammonia gas and thus slowthe loss of ammonia to volatilization, thus making ammonium available toplants in the soil for longer periods of time. In many crops, the amountof nitrogen supplied is critical to the overall quality and growth ofthe crop. Nitrogen is supplied in either urea or ammonium phosphateforms. Due to the high water solubility of these salts, however, much ofthe nitrogen applied is lost to run-off and leaching. In ammonium-basedproducts, if the nitrogen is not lost to leaching or run-off, it isbeing converted to ammonia gas by an enzyme called urease where theammonia can bind to soil particles. Conversion occurring near thesurface of the soil, however, does not allow for binding and thisammonia is lost to the atmosphere. Urease inhibitors are used to protecta farmer's investment in fertilizers by preventing the breakdown of ureaby urease, the soil microbe responsible for converting urea to usableammonia in the soil. This increases the amount of time the nitrogenremains in the soil and is available to the plant for absorption.

Similarly, nitrification inhibitors can be used with a fertilizer (i.e.,incorporated into a urea-containing fertilizer, e.g., urea and ureaammonium nitrate (UAN)) to slow the process of ammonium conversion tonitrate, and subsequently the loss of nitrate to leeching, thus makingammonium available to plants in the soil for longer periods of time.Ammonium is one of the main forms of nitrogen that can be utilized byplants. Increasing the amount of time that the nitrogen is available tothe plant increases the effectiveness of the fertilizer which positivelyimpacts crop yield and quality.

Fertilizers, in one embodiment, are common water soluble inorganicfertilizers that provide nutrients such as phosphorus-based,nitrogen-based, potassium-based or sulphur-based fertilizers. Examplesof such fertilizers include: for nitrogen as the nutrient: nitrates andor ammonium salts such as ammonium nitrate, including in combinationwith urea e.g. as Uram type materials, calcium ammonium nitrate,ammonium sulphate nitrate, ammonium phosphates, particularlymono-ammonium phosphate, di-ammonium phosphate and ammoniumpolyphosphate, ammonium sulphate, and the less commonly used calciumnitrate, sodium nitrate, potassium nitrate and ammonium chloride. It isunderstood that a fertilizer composition can comprise one or acombination of the fertilizers described herein.

A typical urease inhibitor, alkyl thiophosphoric triamide (for example,N-(n-butyl)-thiophosphoric triamide or otherwise “NBPT”), however, facesdrawbacks in its use as NBPT is extremely difficult to handle. NBPT is asticky, waxy, heat and water sensitive material, which cannot be used inits solid form, as it is used at low concentrations making it difficultto evenly distribute on urea prills (i.e., large granules) and in soil.In order to evenly distribute the NBPT onto the urea, the NBPT should bedispersed into a carrier prior to being sprayed onto the urea. Thus, theuse of a solvent system containing the NBPT is desirable as, in itsliquid form, the solvent system is capable of distributing the NBPT intogranular urea (e.g., urea prills) and into liquid fertilizers containingurea. By introducing the NBPT to liquid fertilizers containing urea (forexample, urea-ammonium nitrate solutions or UAN) in a solvent system,the NBPT is capable of being better dispersed in the liquid fertilizer.

Dicyandiamide is useful as a nitrification inhibitor in aqueousagricultural applications, e.g., end use fertilizer compositions, butsimilar to urease inhibitors face similar drawbacks. Nitrificationinhibitors, such as dicyandiamide, generally have very low solubility(about 41 grams per liter (“g/l”)) in water and so it is difficult toincorporate into the aqueous end use fertilizer compositions,particularly under field conditions. As nitrification inhibitors, suchas dicyandiamide, have a generally low solubility, they are used at lowconcentrations in water making it difficult to evenly distribute onurea-containing prills (i.e., large granules) and in soil. In order toevenly distribute the dicyandiamide onto the urea-containing prills orgranules, dicyandiamide should be dispersed into a solvent carrier priorto being sprayed onto the urea. Thus, the use of a solvent systemcontaining dicyandiamide (herein, also termed “DCD”) is desirable as, inits liquid form, the solvent system is capable of distributing thedicyandiamide onto urea granules or prills, urea ammonium nitrategranules or prills or, otherwise, urea-containing granules or prills,and into liquid fertilizers containing urea or urea ammonium nitrate. Byintroducing the dicyandiamide to liquid fertilizers containing urea (forexample, urea-ammonium nitrate solutions or UAN) in a solvent system,the dicyandiamide is capable of being better dispersed in the liquidfertilizer.

In one embodiment, concentrated fertilizer compositions includeconcentrated ammonium nitrate compositions, such as, for example, UAN18, UAN 28, UAN 30 and UAN 32.

Thus, it is desirable to have a solvent system containing alkylthiophosphoric triamide, and in particular, (N-(n-butyl)-thiophosphorictriamide), that has a favorable toxicological and/or ecological profileand desirable characteristics in terms of low volatility,biodegradability or ready biodegradability (i.e., readilybiodegradable), low toxicity or low hazard level. It is desirable tohave a solvent system containing dicyandiamide, that has a favorabletoxicological and/or ecological profile and desirable characteristics interms of low volatility, biodegradability or ready biodegradability(i.e., readily biodegradable), low toxicity or low hazard level. It isalso desirable to have a solvent system containing a combination ofdicyandiamide and an alkyl thiophosphoric triamide, in particular,(N-(n-butyl)-thiophosphoric triamide), that has a favorabletoxicological and/or ecological profile and desirable characteristics interms of low volatility, biodegradability or ready biodegradability(i.e., readily biodegradable), low toxicity or low hazard level.

Another problem is that certain nitrification inhibitors and/or ureaseinhibitors degrade at high temperatures. For example, NBPT—a ureaseinhibitor—degrades rapidly at higher temperature, typically, above 45°C. Often times temperatures in agricultural fields (e.g., corn fields,wheat fields, etc.) reach in excess of 35° C. and sometimes can reach upto 45° C. or higher. For example, at 45° C. NBPT formulated in differentsolvents changes color in days from colorless to a darker green/brown,followed by sludge/precipitate formation after weeks had been exposed tohigh heat. Thus, it is also desirable to have solvent systems containingnitrification inhibitors and/or urease inhibitors that are stabilized athigh temperatures, such as those unitized in hot climates or weather.This invention addresses the addition of stabilizers to prolong thechemical and physical stability of formulated liquid agriculturalcompositions containing (i) one or more nitrification inhibitors, (ii)one or more urease inhibitors or (iii) a combination of both (i) and(ii). In one embodiment, the urease inhibitor is NBPT.

The present invention described herein will become apparent from thefollowing detailed description and examples, which comprises in oneaspect, a liquid composition for use in agricultural applicationscomprising: at least one of a nitrification inhibitor or a ureaseinhibitor; at least one solvent; and at least one amine stabilizer.

In one embodiment, the amine stabilizer is an alkanolamine. In anotherembodiment, the amine stabilizer is a monoalkanolamine. In anotherembodiment, the amine stabilizer is a dialkanolamine. In anotherembodiment, the amine stabilizer is a trialkanolamine. In yet anotherembodiment, the amine stabilizer is a monoethanolamine. In a furtherembodiment, the amine stabilizer is a diethanolamine. In yet a furtherembodiment, the amine stabilizer is a triethanolamine. In anotherembodiment, the alkanol group is chosen from methanol, ethanol,propanol, butanol.

In another aspect, described herein are methods of making a solid orconcentrated liquid fertilizer compositions comprising treating (e.g.,contacting or spray applying) one or more nitrogenous fertilizercompounds with a liquid inhibitor composition. The liquid inhibitorcomposition comprises at least one of a nitrification inhibitor or aurease inhibitor, homogenously dissolved or dispersed in a solventcomprising at least one amine stabilizer as described above. The liquidinhibitor composition, in one embodiment, further comprises at least oneorganic co-solvent selected from polar aprotic solvents, amine solvents,heterocyclic alcohol solvents, and mixtures thereof.

The term treating, in one embodiment, includes spray applying the liquidinhibitor composition with the one or more nitrogenous fertilizercompounds. The term treating, in one embodiment, includes but is notlimited to contacting the inhibitor composition with the one or morenitrogenous fertilizer compounds. In one embodiment, the nitrificationinhibitor is dicyandiamide. In another embodiment, the urease inhibitoris an alkyl thiophosphoric triamide.

In yet another aspect, described herein are concentrated liquidfertilizer compositions comprising, based on weight of the composition:(a) up to about 99 wt %, by weight of composition, of one or morenitrogenous fertilizer compounds, (b) at least one alkyl thiophosphorictriamide or an alkyl thiophosphoric triamide in combination withdicyandiamide, (c) a solvent as described herein and (d) an aminestabilizer.

In a further aspect, described herein are concentrated liquid fertilizercompositions comprising, based on weight of the composition: (a) up toabout 99 wt %, by weight of composition, of one or more nitrogenousfertilizer compounds, (b) at least one of a dicyandiamide or an alkylthiophosphoric triamide, (c) optionally, at least one organophosphatecompound according to formula (I.a), (d) at least one solvent selectedfrom polar aprotic solvents, heterocyclic alcohol solvents, and mixturesthereof, (e) an amine stabilizer and (f) optionally, water. Theconcentrated liquid fertilizer compositions can further comprise one ormore stabilizers.

In yet another aspect, described herein are solid or substantially solidfertilizer compositions comprising: (a) solid particles of one or morenitrogenous fertilizer compounds, and (b) an inhibitor compositioncomprising at least one of a dicyandiamide or an alkyl thiophosphorictriamide supported on at least a portion of the solid particles.

In another aspect, described herein are methods of making a hightemperature stable liquid or aqueous fertilizer composition comprisingcontacting one or more nitrogenous fertilizer compounds, with a liquidinhibitor composition that comprises at least one of a nitrificationinhibitor or a urease inhibitor, homogenously dissolved or dispersed ina solvent comprising an amine stabilizer. In one typical embodiment, theamine stabilizer is monoethanolamine.

The solvent can, optionally, further comprise an organic co-solventselected from polar aprotic solvents, amine solvents, heterocyclicalcohol solvents, and mixtures thereof.

In another aspect, the organophosphate compound has the formula (I.a)

wherein R₁, R₂ and R₃, are each independently chosen from H, a C₁-C₁₆alkyl group, a C₁-C₁₆ alkenyl, group, a C₁-C₁₆ alkoxyalkyl group, aC₇-C₃₀ alkylarylalkyl group, a C₇-C₃₀ arylalkyl group, or an aryl group;provided that at least one of R₁, R₂ or R₃ is not H. In anotherembodiment, R₁, R₂ and R₃, are each independently chosen from H, aC₁-C₁₂ alkyl group, a C₁-C₁₂ alkenyl, group, a C₁-C₁₂ alkoxyalkyl group,a C₇-C₃₀ alkylarylalkyl group, a C₇-C₃₀ arylalkyl group, or an arylgroup; provided that at least one of R₁, R₂ or R₃ is not H. In oneembodiment, R₁, R₂ and R₃, are each independently chosen from H, a C₁-C₄alkyl group, a C₄-C₈ alkyl group, a C₁-C₁₂ alkenyl, group, a C₁-C₄alkoxyalkyl group, a C₇-C₃₀ alkylarylalkyl group, a C₇-C₃₀ arylalkylgroup, or an aryl group; provided that at least one of R₁, R₂ or R₃ isnot H.

In yet another embodiment, R₁, R₂ and R₃, are each independently chosenfrom a C₁-C₁₂ alkyl group, a C₁-C₁₂ alkenyl, group, a C₁-C₁₂ alkoxyalkylgroup, a C₇-C₃₀ alkylarylalkyl group, a C₇-C₃₀ arylalkyl group, or anaryl group. In one embodiment, R₁, R₂ and R₃, are each independentlychosen from a C₁-C₁₂ alkyl group, more typically, a C₂-C₈ alkyl group.

In another aspect, described herein are methods for fertilizing targetplants, comprising applying an aqueous end use fertilizer compositionthat comprises: (a) one or more nitrogenous fertilizer compounds, (b) atleast one of a dicyandiamide or an alkyl thiophosphoric triamide,typically, alkyl thiophosphoric triamide, (c) at least one solventcomprising dimethyl sulfoxide, dimethyl formamide, the dimethyl ester ofsuccinic acid, dimethyl ester of ethyl succinic acid, the dimethyl esterof glutaric acid, the dimethyl ester of methyl glutaric acid, and thedimethyl ester of adipic acid, diethylene triamine, or monoethanolamine,methyl-5-(dimethylamino)-2-methyl-oxopentanoate, dimethylaminoethanol,triethanol amine, a heterocyclic alcohol according to formula (II.a):

or mixtures thereof, (d) an amine stabilizer, and optionally, (e) water,to the target plants or to an environment for the target plants. It isunderstood that the term heterocyclic alcohol includes dioxolanecompounds. The end use fertilizer composition can also comprise, in someembodiments, at least one stabilizer other than an amine stabilizer,which in one embodiment is an organophosphate compound.

In one embodiment, the alkyl thiophosphoric triamide isN-(n-butyl)-thiophosphoric triamide. In another embodiment, the liquidcomposition comprises at least one solvent selected from the groupconsisting of: (a) at least one dioxolane compound of formula (II.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10; b) at least one dibasic ester; c) at least one compound of formula(II.b):

R₃OOC-A-CONR₄R₅   (III),

wherein R₃ comprises a C₁-C₃₆ alkyl group; wherein R₄ and R₅individually comprise a C₁-C₃₆ alkyl group, wherein R₄ and R₅ canoptionally together form a ring; and wherein A is a linear or a brancheddivalent C₂-C₆ alkyl group; d) at least one alkyldimethylamide; e) atleast one alkyl lactate; f) ethyl levulinate; g) at least onealkyoxyalcohol, ether alcohol, amine alcohol, amino alcohol or alcohol;h) at least one glycerine or glycerine derivative; i) at least onealkylene carbonate; j) dimethylsulfoxide; and k) any combinationthereof. In one embodiment, the organic solvent is dimethylsulfoxide.

In another aspect, the present invention is directed to a nitrificationinhibitor composition comprising dicyandiamide dissolved in a liquidmedium that comprises an organic solvent selected from polar aproticsolvents, dibasic esters, amines, amino alcohols, heterocyclic alcohols,and mixtures thereof.

In yet another aspect, the present invention is directed to a method ofmaking a solid or concentrated liquid fertilizer composition comprisingtreating (e.g., contacting, spray applying, brushing, etc) one or morenitrogenous fertilizer compounds with a nitrification inhibitorcomposition that comprises dicyandiamide dissolved in a liquid mediumthat comprises an organic solvent selected from polar aprotic solvents,amine solvents, heterocyclic alcohol solvents, and mixtures thereof.

In a further aspect, the present invention is directed to a concentratedliquid fertilizer composition comprising, by weight of the composition:

-   (a) up to about 99 wt % of one or more nitrogenous fertilizer    compounds,-   (b) an alkyl thiophosphoric triamide or, less typically, a    dicyandiamide (or a combination thereof);-   (c) at least one amine stabilizer as described above (which, in one    embodiment, is monoethanolamine);-   (d) at least one solvent selected from polar aprotic solvents, amine    solvents, heterocyclic alcohol solvents, or mixtures thereof, and-   (d) optionally, water.

In another aspect, the present invention is directed to a concentratedsolid fertilizer composition comprising:

(a) solid particles of one or more nitrogenous fertilizer compounds, and(b) dicyandiamide or an alkyl thiophosphoric triamide supported on atleast a portion of the solid particles.

In one embodiment, the carrier utilized to contact the dicyandiamide oran alkyl thiophosphoric triamide with the solid particles comprises atleast one solvent as described herein and an amine stabilizer asdescribed herein.

In yet another aspect, the present invention is directed to a method ofmaking an high temperature stable, aqueous end use fertilizercomposition comprising contacting one or more nitrogenous fertilizercompounds with a urease inhibitor composition that comprises an alkylthiophosphoric triamide dissolved in a liquid medium that comprises anorganic solvent selected from polar aprotic solvents, amine solvents,heterocyclic alcohol solvents, or mixtures thereof, in addition to anamine stabilizer. In one embodiment, the amine stabilizer inmonoethanolamine. In another embodiment, the amine stabilizer isdiethanolamine. In yet another embodiment, the amine stabilizer istriethanolamine.

In a further aspect, the present invention is directed to a method forfertilizing target plants, comprising applying an aqueous end usefertilizer composition that comprises:

-   (a) one or more nitrogenous fertilizer compounds;-   (b) dicyandiamide, an alkyl thiophosphoric triamide, or a mixture    thereof;-   (c) an amine stabilizer (which is, in on embodiment,    monoethanolamine),-   (d) at least one organic solvent selected from dimethyl sulfoxide,    dimethyl formamide, the dimethyl ester of succinic acid, dimethyl    ester of ethyl succinic acid, the dimethyl ester of glutaric acid,    the dimethyl ester of methyl glutaric acid, and the dimethyl ester    of adipic acid, diethylene triamine, or monoethanolamine,    methyl-5-(dimethylamino)-2-methyl-oxopentanoate,    dimethylaminoethanol, triethanol amine, a heterocyclic alcohol    according to formula (II.a):

Or mixtures thereof; and

-   (e) optionally, water,

to the target plants or to an environment for the target plants.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a photograph of Several amines or amides were tested to checkif they can stabilize NBPT degradation at high temperatures (at greaterthan 45° C.) in NBPT/DMSO formulation. Each sample was prepared with 2%of amine stabilizer added.

FIG. 2 is a photograph showing the results from 10 weeks storage of 2%monoethanolamine in 1:1 NBPT:DMSO at two different temperatures, 45° C.and Room Temperature (20° C.).

FIG. 3. is a chart of the degradation product, i.e., dimethyl sulfide(DMS) in parts per million (ppm), measured at varying high temperaturesfor a period of weeks. The results indicate the liquid fertilizercomposition with the amine stabilizer exhibited higher stability overtime versus a liquid fertilizer composition without the stabilizer.

DETAILED DESCRIPTION

As used herein, the term “alkyl” means a saturated straight chain,branched chain, or cyclic hydrocarbon radical, including but not limitedto, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl,pentyl, n-hexyl, and cyclohexyl.

As used herein, the term “aryl” means a monovalent unsaturatedhydrocarbon radical containing one or more six-membered carbon rings inwhich the unsaturation may be represented by three conjugated doublebonds, which may be substituted one or more of carbons of the ring withhydroxy, alkyl, alkenyl, halo, haloalkyl, or amino, including but notlimited to, phenoxy, phenyl, methylphenyl, dimethylphenyl,trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl, andtristyrylphenyl.

As used herein, the term “alkylene” means a divalent saturated straightor branched chain hydrocarbon radical, such as for example, methylene,dimethylene, trimethylene.

As used herein, the term “alkoxyl” means an oxy radical that issubstituted with an alkyl group, such as for example, methoxyl, ethoxyl,propoxyl, isopropoxyl, or butoxyl, which may optionally be furthersubstituted on one or more of the carbon atoms of the radical.

As used herein, the term “alkoxyalkyl” means an alkyl radical that issubstituted with one or more alkoxy substituents, more typically a(C₁-C₂₂)alkyloxy-(C₁-C₆)alkyl radical, such as methoxymethyl, andethoxybutyl.

As used herein, the term “alkenyl” means an unsaturated straight orbranched hydrocarbon radical, more typically an unsaturated straight,branched, (which, in one particular embodiment, is C₁-C₇₅) hydrocarbonradical, that contains one or more carbon-carbon double bonds, such as,for example, ethenyl, n-propenyl, iso-propenyl.

As used herein, the term “arylalkyl” means an alkyl group substitutedwith one or more aryl groups, more typically a (C₁-C₁₈)alkyl substitutedwith one or more (C₆-C₁₄)aryl substituents, such as, for example,phenylmethyl, phenylethyl, and triphenylmethyl.

As used herein, the term “aryloxy” means an oxy radical substituted withan aryl group, such as for example, phenyloxy, methylphenyl oxy,isopropylmethylphenyloxy.

As used herein, the terminology “(C_(r)-C_(s))” in reference to anorganic group, wherein r and s are each integers, indicates that thegroup may contain from r carbon atoms to s carbon atoms per group.

Dicyandiamide is a known compound according to formula (I.b):

Dicyandiamide, also known as “2-cyanoguanidine”, is typically made bytreating cyanamide with base and is commercially available.

In one embodiment, the compositions according to the present inventioncomprise a urease inhibitor, such as an alkyl thiophosphoric triamide orammonium thiosulfate, a nitrification inhibitor, or a combination ofboth a urease inhibitor and a nitrification inhibitor.

In one embodiment, alkyl thiophosphoric triamide isN-(n-butyl)-thiophosphoric triamide (“NBPT”). The at least one of alkylthiophosphoric triamide or dicyandiamide or combination thereof can bepresent in the liquid agricultural composition at a lower range of 2% byweight of the composition. In another embodiment, the at least one ofalkyl thiophosphoric triamide or dicyandiamide or combination thereofcan be present in the liquid agricultural composition at a lower rangeof 3% by weight of the composition. The at least one of alkylthiophosphoric triamide or dicyandiamide or combination thereof can bepresent in the liquid agricultural composition at a lower range of 5% byweight of the composition.

In another embodiment, at least one of alkyl thiophosphoric triamideand/or dicyandiamide can be present in the liquid agriculturalcomposition at a lower range of 0.5%, or 1%, or 2%, or 3%, or 4%, or 5%,6%, or 8%, or 10% or 12% or 14%, by weight of the composition. The atleast one of alkyl thiophosphoric triamide or dicyandiamide orcombination thereof can be present in the liquid agriculturalcomposition at an upper range of 75%, or 65%, or 60% by weight of thecomposition. In another embodiment, the at least one of alkylthiophosphoric triamide or dicyandiamide or combination thereof can bepresent in the liquid agricultural composition at an upper range of 60%by weight of the composition. In another embodiment, the at least one ofalkyl thiophosphoric triamide or dicyandiamide or combination thereofcan be present in the liquid agricultural composition at an upper rangeof 55% by weight of the composition. In another embodiment, at least oneof alkyl thiophosphoric triamide and/or dicyandiamide can be present inthe liquid agricultural composition at an upper range of 59%, or 57%, or55% or 53% or 50%, by weight of the composition. In another embodiment,at least one of alkyl thiophosphoric triamide and/or dicyandiamide canbe present in the liquid agricultural composition at an upper range of48%, or 46%, or 45% or 42% or 40%, by weight of the composition.

In some embodiments, the dibasic ester or blend of dibasic esterscomprises adducts of alcohol and linear diacids, the adducts having theformula (IV):

R—OOC-A-COO—R   (IV)

wherein R is an alkyl group (e.g., methyl, ethyl, etc.) and A is amixture of —(CH2)4-, —(CH2)3, and —(CH2)2-. In other embodiments, theblend comprises adducts of alcohol, typically ethanol, and lineardiacids, the adducts having the formula R1-OOC-A-COO—R2, wherein atleast part of R1 and/or R2 are residues of at least one linear alcoholhaving 4 carbon atoms, and/or at least one linear or branched alcoholhaving at least 5 carbon atoms, and wherein A is a divalent linearhydrocarbon. In some embodiments A is one or a mixture of —(CH2)4-,—(CH2)3, and —(CH2)2-. In other embodiments, the dibasic ester comprisesadducts of an alcohol and linear or branched diacids, the adducts havingthe formula (IV): R—OOC-A-COO—R, wherein R is an alkyl group (e.g.,methyl, ethyl, etc.) and A one of the following: —(CH2)4-, —(CH2)3,—(CH2)2-, —CH2-, or any mixture thereof.

Dibasic esters of the present invention may be derived from one or moreby-products in the production of polyamide, for example, polyamide 6,6.In one embodiment, the at least one dibasic ester comprises a blend oflinear or branched, cyclic or noncyclic, C1-C20 alkyl, aryl, alkylarylor arylalkyl esters of adipic diacids, glutaric diacids, and succinicdiacids. In another embodiment, the composition comprises a blend oflinear or branched, cyclic or noncyclic, C1-C20 alkyl, aryl, alkylarylor arylalkyl esters of adipic diacids, methylglutaric diacids, andethylsuccinic diacids

Generally, polyamide is a copolymer prepared by a condensation reactionformed by reacting a diamine and a dicarboxylic acid. Specifically,polyamide 6,6 is a copolymer prepared by a condensation reaction formedby reacting a diamine, typically hexamethylenediamine, with adicarboxylic acid, typically adipic acid.

In one embodiment, the blend of dibasic esters can be derived from oneor more by-products in the reaction, synthesis and/or production ofadipic acid utilized in the production of polyamide, the compositioncomprising a blend of dialkyl esters of adipic diacids, glutaricdiacids, and succinic diacids (herein referred to sometimes as “AGS” orthe “AGS blend”).

In one embodiment, the blend of esters is derived from by-products inthe reaction, synthesis and/or production of hexamethylenediamineutilized in the production of polyamide, typically polyamide 6,6. Thecomposition comprises a blend of dialkyl esters of adipic diacids,methylglutaric diacids, and ethylsuccinic diacids (herein referred tosometimes as “MGA”, “MGN”, “MGN blend” or “MGA blend”).

In certain embodiments, the dibasic ester blend comprises:

a diester of formula (IV.a):

a diester of formula (IV.b):

and

a diester of formula (IV.c):

R1 and/or R2 can individually comprise a hydrocarbon having from about 1to about 8 carbon atoms, typically, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, n-butyl, isoamyl, hexyl, heptyl or octyl. In suchembodiments, the blend typically comprises (by weight of the blend) (i)about 15% to about 35% of the diester of formula (IV.a), (ii) about 55%to about 70% of the diester of formula (IV.b), and (iii) about 7% toabout 20% of the diester of formula (IV.c), and more typically, (i)about 20% to about 28% of the diester of formula (IV.a), (ii) about 59%to about 67% of the diester of formula (IV.b), and (iii) about 9% toabout 17% of the diester of formula (IV.c). The blend is generallycharacterized by a flash point of 98° C., a vapor pressure at 20° C. ofless than about 10 Pa, and a distillation temperature range of about200-300° C.

In certain other embodiments, the dibasic ester blend comprises:

a diester of the formula (IV.d):

a diester of the formula (IV.e):

and, optionally,

a diester of the formula (IV.c):

R1 and/or R2 can individually comprise a hydrocarbon having from about 1to about 8 carbon atoms, typically, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, n-butyl, isoamyl, hexyl, heptyl, or octyl. In suchembodiments, the blend typically comprises (by weight of the blend) (i)from about 5% to about 30% of the diester of formula (IV.d), (ii) fromabout 70% to about 95% of the diester of formula (IV.e), and (iii) fromabout 0% to about 10% of the diester of formula (IV.c). More typically,the blend typically comprises (by weight of the blend): (i) from about6% to about 12% of the diester of formula (IV.d), (ii) from about 86% toabout 92% of the diester of formula (IV.e), and (iii) from about 0.5% toabout 4% of the diester of formula (IV.c).

Most typically, the blend comprises (by weight of the blend): (i) about9% of the diester of formula (IV.d), (ii) about 89% of the diester offormula (IV.e), and (iii) about 1% of the diester of formula (IV.c). Theblend is generally characterized by a flash point of 98° C., a vaporpressure at 20° C. of less than about 10 Pa, and a distillationtemperature range of about 200-275° C.

In another embodiment, the at least one of alkyl thiophosphoric triamideor dicyandiamide or combination thereof can be present in the liquidagricultural composition at an upper range of 70% by weight of thecomposition. In another embodiment, the at least one of alkylthiophosphoric triamide or dicyandiamide or combination thereof can bepresent in the liquid agricultural composition at an upper range of 65%by weight of the composition. In another embodiment, the at least one ofalkyl thiophosphoric triamide or dicyandiamide or combination thereofcan be present in the liquid agricultural composition at an upper rangeof 60% by weight of the composition. In another embodiment, the at leastone of alkyl thiophosphoric triamide or dicyandiamide or combinationthereof can be present in the liquid agricultural composition at anupper range of 55% by weight of the composition. In another embodiment,the at least one of alkyl thiophosphoric triamide or dicyandiamide orcombination thereof can be present in the liquid agriculturalcomposition at an upper range of 40% by weight of the composition. Inanother embodiment, the at least one of alkyl thiophosphoric triamide ordicyandiamide or combination thereof can be present in the liquidagricultural composition at an upper range of 35% by weight of thecomposition. In another embodiment, the at least one of alkylthiophosphoric triamide or dicyandiamide or combination thereof can bepresent in the liquid agricultural composition at an upper range of 30%by weight of the composition. In another embodiment, the at least one ofalkyl thiophosphoric triamide or dicyandiamide or combination thereofcan be present in the liquid agricultural composition at an upper rangeof 25% by weight of the composition.

In another embodiment, the at least one of alkyl thiophosphoric triamideor dicyandiamide can be present in the liquid agricultural compositionin an amount between about 7% by weight of the composition to about 55%by weight of the composition. In another embodiment, the at least one ofalkyl thiophosphoric triamide or dicyandiamide can be present in thecomposition in an amount between about 8% by weight of the compositionto about 50% by weight of the composition. In another embodiment, the atleast one of alkyl thiophosphoric triamide or dicyandiamide can bepresent in the liquid agricultural composition in an amount betweenabout 7% by weight of the composition to about 45% by weight of thecomposition. In another embodiment, the at least one of alkylthiophosphoric triamide or dicyandiamide can be present in the liquidagricultural composition in an amount between about 7% by weight of thecomposition to about 40% by weight of the composition. In anotherembodiment, the at least one of alkyl thiophosphoric triamide ordicyandiamide can be present in the liquid agricultural composition inan amount between about 7% by weight of the composition to about 35% byweight of the composition.

The at least one of alkyl thiophosphoric triamide or dicyandiamide canbe present in the composition in an amount between about 0.5% by weightof the composition and about 60% by weight of the composition or, inanother embodiment, can be present in the composition in an amountbetween about 1% by weight of the composition and about 40% by weight ofthe composition, and, in another embodiment, can be present in thecomposition in an amount between about 0.5% by weight of the compositionand about 20% by weight of the composition. In one particularembodiment, the at least one of alkyl thiophosphoric triamide ordicyandiamide is present in the composition in an amount between about1% by weight of the composition and about 30% by weight of thecomposition. The at least one of alkyl thiophosphoric triamide ordicyandiamide means that alkyl thiophosphoric triamide can be solelypresent, dicyandiamide can be solely present, or a combination of alkylthiophosphoric triamide and dicyandiamide is present.

Compounds suitable as the amine stabilizer component of the compositionand methods of the present invention are alkanolamines. In anotherembodiment, the amine stabilizer is a monoalkanolamine. In anotherembodiment, the amine stabilizer is a dialkanolamine. In anotherembodiment, the amine stabilizer is a trialkanolamine. In yet anotherembodiment, the amine stabilizer is a monoethanolamine. In a furtherembodiment, the amine stabilizer is a diethanolamine. In yet a furtherembodiment, the amine stabilizer is a triethanolamine. In anotherembodiment, the alkanol group is chosen from methanol, ethanol,propanol, butanol. The amine stabilizer component forms stablecompositions at high temperatures with the nitrification and/or ureaseinhibitor, which in some embodiments means stability at temperaturesranging from −16° C. to 54° C., in other embodiments, −10° C. to 40° C.,in other embodiments, −5° C. to 40° C., in other embodiments, −2° C. to40° C., or in other embodiments, 0° C. to 40° C.

In another embodiment, compounds suitable as the organic solvent arepolar aprotic solvents, heterocyclic alcohol solvents, and/or mixturesthereof, that form liquid, or otherwise stable, compositions with thenitrification and/or urease inhibitor at temperatures at or greater than−16° C., in alternative embodiments, greater than −14° C., in otherembodiments, greater than −12° C., in other embodiments, greater than−10° C., in further embodiments, greater than −8° C., in otherembodiments, greater than −5° C., in other embodiments, greater than −3°C., in other embodiments, greater than −2° C., in other embodiments,greater than 0° C., in other embodiments, greater than 2° C., in otherembodiments, greater than 4° C., in other embodiments, greater than 5°C.

In some embodiments, at high temperature ranges or at greater than aspecified temperature (as described herein), the liquid fertilizercomposition is stable, meaning the urease and/or nitrificationinhibitor(s) do not react with the solvent or solvent component underanticipated manufacturing, storage, and use conditions. In oneembodiment, the liquid fertilizer compositions are stable at atemperature greater than 25° C. In one embodiment, the liquid fertilizercompositions are stable at a temperature greater than 27° C. In oneembodiment, the liquid fertilizer compositions are stable at atemperature greater than 29° C. In one embodiment, the liquid fertilizercompositions are stable at a temperature greater than 30° C. In oneembodiment, the liquid fertilizer compositions are stable at atemperature greater than 32° C. In one embodiment, the liquid fertilizercompositions are stable at a temperature greater than 34° C. In oneembodiment, the liquid fertilizer compositions are stable at atemperature greater than 35° C. In one embodiment, the liquid fertilizercompositions are stable at a temperature greater than 37° C. In oneembodiment, the liquid fertilizer compositions are stable at atemperature greater than 40° C. In one embodiment, the liquid fertilizercompositions are stable at a temperature greater than 42° C. In oneembodiment, the liquid fertilizer compositions are stable at atemperature greater than 44° C. In one embodiment, the liquid fertilizercompositions are stable at a temperature greater than 45° C. In oneembodiment, the liquid fertilizer compositions are stable at atemperature greater than 47° C. In one embodiment, the liquid fertilizercompositions are stable at a temperature greater than 50° C.

In one embodiment, at the specified temperature ranges or at greaterthan a specified temperature (as described herein), the liquidfertilizer composition is stable, meaning the liquid fertilizercomposition is or substantially is in one phase, i.e., no visiblecrystals, no visible precipitation, and/or no visible multiple liquidphases. In another embodiment, the liquid fertilizer composition isstable, meaning the liquid fertilizer composition is or substantially isin one phase and shows little or slight discoloration.

In one embodiment, the liquid fertilizer compositions contains anorganophosphate compound according to formula (I.a) (wherein R₁, R₂ andR₃ are as described above).

Suitable polar aprotic organic solvents include, for example,dichloromethane, dimethyl acetamide, dimethyl formamide, dimethylsulfoxide, ethyl acetate, hexamethylphosphoramide, dimethyl sulfone,sulfolane, 1,3-dimethyl-2-imidazoidinone,1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone, methyl acetate, ethyllactate, methylpyrrolidone, tetrahydrofuran, propylene carbonate, anddibasic ester solvents.

Suitable dibasic ester solvents include, for example, dialkyl esters ofdicarboxylic acids, more typically, the di(C₁-C₁₂)alkyl esters ofsaturated linear or branched (C₂-C₈)aliphatic carboxylic acids or amixture thereof. In one embodiment, the dibasic ester componentcomprises one or more compounds according to formula (III):

R¹OOC-A-CONR²R³  (III)

wherein:

-   -   A is a divalent linear or branched (C₂-C₈)aliphatic group, and    -   R¹, R², and R³ are each independently (C₁-C₁₂)alkyl,        (C₁-C₁₂)aryl, (C₁-C₁₂)alkaryl or (C₁-C₁₂)arylalkyl, and R² and        R³ may each optionally be substituted with one or more hydroxyl        groups.

In one embodiment, the dibasic ester solvent component of thecompositions and methods of the present invention comprises one or moredimethyl esters of saturated linear or branched (C₄-C₆)aliphaticcarboxylic acids, such the dimethyl ester of succinic acid, dimethylester of ethyl succinic acid, the dimethyl ester of glutaric acid, thedimethyl ester of methyl glutaric acid, and the dimethyl ester of adipicacid, and mixtures thereof. In one embodiment, the dibasic estercomponent comprises the dimethyl ester of succinic acid, the dimethylester of glutaric acid, and optionally, the dimethyl ester of adipicacid, In another embodiment, the dibasic ester component comprises thedimethyl ester of ethyl succinic acid, the dimethyl ester of methylglutaric acid, and optionally, the dimethyl ester of adipic acid.

In one embodiment, the dibasic ester solvent component of thecompositions and methods of the present invention comprises one or moredialkyl esters of saturated linear or branched (C₄-C₆)aliphaticcarboxylic acids, such the dialkyl ester of succinic acid, dialkyl esterof ethylsuccinic acid, the dialkyl ester of glutaric acid, the dialkylester of methylglutaric acid, and the dialkyl ester of adipic acid, andmixtures thereof. In one embodiment, the dibasic ester componentcomprises the dialkyl ester of succinic acid, the dialkyl ester ofglutaric acid, and optionally, the dimethyl ester of adipic acid, Inanother embodiment, the dibasic ester component comprises the dialkyldimethyl ester of ethylsuccinic acid, the dialkyl ester ofmethylglutaric acid, and optionally, the dialkyl ester of adipic acid.Each alkyl group in the dialkyl group, one embodiment, individuallycomprise a C₁-C₈ alkyl. In another embodiment, each alkyl group in thedialkyl group, one embodiment, individually comprise a C₁-C₄ alkyl. Inanother embodiment, each alkyl group in the dialkyl group, oneembodiment, individually comprise a C₁-C₆ alkyl.

Suitable amine solvents include primary amines, includingmonoalkylamines, such as propylamine, secondary amines, includingdialkyl amines and diaryl amines, such as dimethylamine anddiphenylamine, and tertiary amines, such as diethylene triamine andmethyl-5-(dimethylamino)-2-methyl-oxopentanoate.

In one embodiment, the amine solvent component of the compositions andmethods of the present invention is selected from aliphatic or aromaticprimary, secondary, or tertiary amines may optionally further compriseone or more additional functional groups, such as hydroxyalkyl groups,hydroxyl groups, carbonyl groups, or alkyl ester groups, other than oneor more amino groups.

In one embodiment, the organic solvent component of the compositions andmethods of the present invention comprises an amino alcohol. Compoundssuitable as the amino alcohol solvent component of the compositions andmethods of the present invention are those compounds that comprise atleast one primary, secondary, or tertiary amino moiety per molecule andat least one hydroxyalkyl moiety per molecule, more typically In oneembodiment, the amino alcohol is a linear, branched, or cyclic,saturated or unsaturated hydrocarbon that is substituted on at least onecarbon atom with an amino group and on at least one other carbon atomwith hydroxyalkyl or hydroxyl group, such as monoethanolamine,ethylaminoethanol, dimethylaminoethanol, isopropylaminoethanol,diethanolamine, triethanolamine, methylaminoethanol, aminopropanol,methylaminopropanol, dimethylaminopropanol, aminobutanol,dimethylaminobutanol, aminobutanediol, trihydroxymethylaminoethane,diethylaminopropanediol, 1-amino-cyclopentane methanol, and aminobenzylalcohol, or a heterocyclic ring that comprises at least one nitrogenatom as a ring member and/or is substituted on at least one carbon atomwith an amino group and that is substituted on at least one other carbonatom with a hydroxyalkyl or hydroxyl group, such asmethylaminomethyl-1,3-dioxolane.

Suitable heterocyclic alcohol solvents include, for example, 5- or6-membered heterocyclic rings that include 1 or 2 oxygen atoms as ringmember, that are substituted on at least one carbon atom of the ringwith a (C₁-C₆)hydroxyalkyl group, and that may optionally be substitutedon one or more carbon atoms of the ring with one or more (C₁-C₄)alkylgroups. It is understood that the term heterocyclic alcohol includesdioxolane compounds. In one embodiment, the heterocyclic alcoholcomponent of the present invention comprises a one or more compoundsselected from heterocyclic alcohols according to formulas (II.c),(II.d), (II.e), (II.f), and (II.g):

In one embodiment, the organic solvent component comprises one or moredibasic ester compounds according to any of formula (III) or formula(IV), one or more amino alcohols, one or more tertiary amines, one ormore heterocyclic alcohols according to formulas (II.a-II.g), ormixtures thereof.

In one embodiment, the organic solvent component of the composition andmethods of the present invention comprises dimethyl sulfoxide, dimethylformamide, the dimethyl ester of succinic acid, dimethyl ester of ethylsuccinic acid, the dimethyl ester of glutaric acid, the dimethyl esterof methyl glutaric acid, and the dimethyl ester of adipic acid,diethylene triamine, or monoethanolamine,methyl-5-(dimethylamino)-2-methyl-oxopentanoate, dimethylaminoethanol,triethanol amine, a heterocyclic alcohol according to any of formulas(II.a-II.g), or a mixture thereof.

In one embodiment, the organic solvent component of the composition andmethods of the present invention comprises dimethyl sulfoxide, dimethylformamide, diethylene triamine, monoethanolamine, or a mixture thereof.

In one embodiment, the organic solvent component of the composition andmethods of the present invention comprises a mixture of at least oneorganophosphate solvent according to formula (I.a), wherein R₁, R₂ andR₃ are as described above, and dimethyl sulfoxide.

In one embodiment, a compound utilized as the solvent or as a componentin the solvent blend is a compound of general formula (III):

R₃OOC-A-CONR₄R₅   (III),

According to one embodiment, the expression “compound” denotes anycompound corresponding to the general formula (III). In otherembodiments, the term “compound” also refers to mixtures of severalmolecules corresponding to general formula (III). It may therefore be amolecule of formula (III) or a mixture of several molecules of formula(III), wherein both fall under the definition of the term “compound”when referring to formula (III).

The R₃, R₄ and R₅ groups can be, in some embodiments, identical or, inother embodiment, different. In one embodiment, may be groups chosenfrom C₁-C₂₀ alkyl, aryl, alkaryl or arylalkyl groups or the phenylgroup. In another embodiment, may be groups chosen from C₁-C₁₂ alkyl,aryl, alkaryl or arylalkyl groups or the phenyl group. Mention is madeespecially of Rhodiasolv® PolarClean (Manufactured by Solvay USA Inc.,Cranbury, N.J.). The R₄ and R₅ groups may optionally be substituted. Inone particular embodiment, the groups are substituted with hydroxylgroups.

In one embodiment, R₃ group is chosen from methyl, ethyl, propyl,isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, isoamyl, n-hexyl,cyclohexyl, 2-ethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, tridecylgroups.

R₄ and R₅ groups, which are identical or different, in one embodiment,may especially be chosen from methyl, ethyl, propyl (n-propyl),isopropyl, n-butyl, isobutyl, n-pentyl, amyl, isoamyl, hexyl, cyclohexylor hydroxyethyl groups. The R₄ and R₅ groups may also be such that theyform, together with the nitrogen atom, a morpholine, piperazine orpiperidine group. According to some embodiments, R₄ and R₅ are eachmethyl, or R₄ and R₅ are each ethyl, or R₄ and R₅ are each hydroxyethyl.

According to one embodiment, if A comprises a linear group of formula—CH₂—CH₂— and/or of formula —CH₂—CH₂—CH₂—CH₂— and/or of formula —(CH₂)₈—then it is a mixture of A groups. According to one particularembodiment, if A is linear, then it is a mixture of A groups, forexample a mixture of two or three —CH₂—CH₂— (ethylene); —CH₂—CH₂—CH₂—(n-propylene); and —CH₂—CH₂—CH₂—CH₂— (n-butylene) groups (or isomersthereof).

According to a first particular embodiment of the invention, the A groupis a divalent linear alkyl group chosen from the groups of the followingformulae: —CH₂—CH₂— (ethylene); —CH₂—CH₂—CH₂— (n-propylene);—CH₂—CH₂—CH₂—CH₂— (n-butylene), and mixtures thereof.

In one embodiment, the inhibitor composition of the present inventioncomprises, based on 100 parts by weight (“pbw”) of the composition:

from about 4 to about 60 pbw, more typically from about 10 to about 55pbw, and even more typically from about 20 to about 40 pbwdicyandiamide, and

from about 55 to about 96 pbw, more typically from about 58 to about 90pbw, and even more typically from about 60 to about 80 pbw of theorganic solvent.

In one embodiment, the inhibitor composition of the present inventioncomprises one or more urease inhibitors, such as, for example, NBPT orammonium thiosulfate.

The nitrogenous fertilizer compound is treated with the inhibitorcomposition by contacting the nitrogenous fertilizer composition withthe inhibitor composition described herein (e.g., nitrificationinhibitor or urease inhibitor or a combination of both). The nitrogenousfertilizer composition may be in solid or liquid form.

Suitable nitrogenous fertilizers are those containing a nitrogenouscompound such as urea, nitrate salts, ammonium salt, or a mixturethereof, such as ammonium nitrate, ammonium sulfate, ammoniumthiosulfate, ammonium polysulfide, ammonium phosphates, ammoniumchloride, ammonium bicarbonate, anhydrous ammonia, calcium nitrate,nitrate soda, calcium cyanamide. In one embodiment, the nitrogenousfertilizer comprises ammonium nitrate. Suitable ammoniumnitrate-containing fertilizers include, for example, UAN 18, UAN 28, andUAN 30.

In one embodiment, the nitrogenous fertilizer composition is in solidparticulate form, and the contacting of the nitrogenous fertilizercomposition with the inhibitor composition is conducted by, for example,spraying the composition of the present invention on the particles ofsolid fertilizer composition.

In one embodiment, the concentrated fertilizer composition of thepresent invention is a solid nitrification-inhibited fertilizercomposition that comprises, based on 100 pbw of the composition:

from about 60 pbw to about 99.999, more typically from about 70 pbw toabout 99.999, and even more typically from about 80 pbw to about 99.999solid particles of one or more nitrogenous fertilizer compounds, and

from about 0.001 to about 40 pbw, more typically from about 0.001 toabout 30 pbw, and even more typically from about 0.001 to about 20 pbw,dicyandiamide.

In one embodiment, the solid nitrification-inhibited fertilizercomposition of the present invention further comprises one or moreurease inhibitors, more typically NBPT.

In one embodiment, the end use fertilizer composition of the presentinvention is made by combining the inhibitor composition of the presentinvention with a solid nitrogenous fertilizer to form a solidnitrification-inhibited fertilizer composition and subsequentlydissolving the solid nitrification-inhibited fertilizer composition inan aqueous medium, typically water, in a ratio of up to about 500 pbw,more typically from 100 to 500 pbw and even more typically from about100 to about 300 pbw, of the aqueous medium per 1 pbw of the solidnitrification-inhibited fertilizer composition.

In one embodiment, the fertilizer compound is in liquid form and thecontacting of the fertilizer composition with the inhibitor compositionis conducted by mixing the inhibitor composition with the liquidfertilizer composition.

In one embodiment, the concentrated fertilizer composition of thepresent invention is a concentrated liquid nitrification-inhibitedfertilizer composition that comprises, based on 100 pbw of thecomposition:

from about 20 to about 99.989 pbw, more typically from about 30 to about99.985 pbw, and even more typically from about 40 to about 99.98 pbw ofone or more nitrogenous fertilizer compounds,

from about 0.001 to 40 pbw, more typically from about 0.005 to 30 pbw,and even more typically from about 0.01 to 20 pbw NBPT (or NBPT incombination with DCD), and

from about 0.01 to 60 pbw, more typically from about 0.01 to about 40pbw, and even more typically from about 0.01 to about 30 pbw of theorganic solvent or solvent mixture, as described herein.

In one embodiment, the concentrated liquid nitrification-inhibitedfertilizer composition of the present invention further comprises one ormore urease inhibitors, more typically NBPT.

In one embodiment, the end use fertilizer composition of the presentinvention is made by combining the inhibitor composition of the presentinvention with a concentrated nitrogenous fertilizer to form aconcentrated liquid nitrification-inhibited fertilizer composition andsubsequently diluting the concentrated liquid nitrification-inhibitedfertilizer composition with an aqueous medium, typically water in aratio of up to about 500 pbw, more typically from about 10 to about 500pbw and even more typically from about 100 to about 300 pbw, of theaqueous medium per 1 pbw concentrated liquid nitrogenous fertilizercomposition.

In one embodiment, the end use fertilizer composition of the presentinvention is made by combining the inhibitor composition of the presentinvention, a solid or concentrated liquid nitrogenous fertilizer, and anaqueous medium.

In one embodiment, the end use fertilizer composition of the presentinvention is an aqueous liquid composition that comprises water, one ormore nitrogenous fertilizer compounds, and dicyandiamide, typically inan amount of from 2×10⁻⁶ pbw to about 4 pbw dicyandiamide per 100 pbw ofthe end use fertilizer composition.

In one embodiment, the end use fertilizer composition of the presentinvention comprises water and based on 100 parts by weight of thecomposition:

from about 0.04 to about 10 pbw, more typically from about 0.06 to about10 pbw, and even more typically from about 0.08 pbw to about 10 pbw toof one or more nitrogenous fertilizer compounds,

from about 2×10⁻⁶ to about 4 pbw, more typically from about 1×10⁻⁵ toabout 3 pbw, and even more typically from about 2×10⁻⁴ to about 2 pbwdicyandiamide, and

from about 2×10⁻⁴ to about 6 pbw, more typically from about 2×10⁻⁴ toabout 4 pbw, and even more typically from about 2×10⁻⁴ to about 3 pbw ofthe organic solvent.

In one embodiment, the end use fertilizer composition of the presentinvention comprises one or more urease inhibitors, more typically NBPT,alone or in combination with the nitrification inhibitor.

In one embodiment, the end use fertilizer composition of the presentinvention comprises from about 0.001 to about 5 pbw, more typically fromabout 0.01 to about 2 pbw dicyandiamide per 100 pbw of the one or morenitrogenous fertilizer compounds.

In one embodiment, the end use fertilizer composition is applied totarget plants or to an environment for the target plants, i.e., toground on or within which the target plants are growing or to be grown,at a rate of from about 0.01 pounds to about 5 pounds of the fertilizercomposition, more typically from about 0.05 pounds to about 2 pounds ofthe fertilizer composition, per 100 square feet of ground.

In one embodiment, the end use fertilizer composition is applied totarget plants or to an environment for the target plants at a rateeffective to provide a dosage of nitrogenous fertilizer compound of fromabout 0.01 pounds to about 5 pounds of fertilizer compound, moretypically from about 0.05 pounds to 2 pounds of fertilizer compound, per100 square feet of ground.

In one embodiment, the end use fertilizer composition is applied totarget plants or to an environment for the target plants at a rateeffective to provide a dosage of dicyandiamide of from about 0.01 poundsto 5 pounds of dicyandiamide, more typically from about 0.05 pounds to 2pounds of dicyandiamide, per 1000 square feet of ground.

The composition of the present invention provides improved ease ofhandling of dicyandiamide, improved solubility characteristics, lowtoxicity of the organic solvents; good storage characteristics, andexcellent miscibility with aqueous compositions, such as aqueousnitrogenous fertilizer formulations.

In one embodiment the composition comprises, by weight of composition,greater than 50 wt % of DCD and/or NBPT, the remainder being solvent ora mixture of solvents with the amine stabilizer. By way of example, inone embodiment, the fertilizer composition comprises, by weight ofcomposition, 50 wt % of DCD and 50 wt % of a solvent blend of DMSO andat least one amine stabilizer as described above.

In one embodiment the composition comprises, by weight of composition,greater than 50 wt % of NBPT, the remainder being solvent or a mixtureof solvents with the amine stabilizer. In one embodiment the compositioncomprises, by weight of composition, greater than 51 wt %, 52 wt %, 53wt %, 54 wt % of NBPT, the remainder being solvent or a mixture ofsolvents with the amine stabilizer. In one embodiment the compositioncomprises, by weight of composition, greater than 55 wt %, 56 wt %, 57wt %, 58 wt %, 59 wt % of NBPT, the remainder being solvent or a mixtureof solvents with the amine stabilizer. In one embodiment the compositioncomprises, by weight of composition, greater than 60 wt % of NBPT, theremainder being solvent or a mixture of solvents with the aminestabilizer. In one embodiment the composition comprises, by weight ofcomposition, greater than 65 wt % of NBPT, the remainder being solventor a mixture of solvents with the amine stabilizer. In one embodimentthe composition comprises, by weight of composition, greater than 70 wt% of NBPT, the remainder being solvent or a mixture of solvents with theamine stabilizer. In one embodiment the composition comprises, by weightof composition, greater than 75 wt % of NBPT, the remainder beingsolvent or a mixture of solvents with the amine stabilizer.

In one embodiment the composition comprises, by weight of composition,greater than 50 wt % of NBPT in combination with DCD, the remainderbeing solvent or a mixture of solvents with the amine stabilizer. In oneembodiment the composition comprises, by weight of composition, greaterthan 51 wt %, 52 wt %, 53 wt %, 54 wt % of NBPT in combination with DCD,the remainder being solvent or a mixture of solvents with the aminestabilizer. In one embodiment the composition comprises, by weight ofcomposition, greater than 55 wt %, 56 wt %, 57 wt %, 58 wt %, 59 wt % ofNBPT in combination with DCD, the remainder being solvent or a mixtureof solvents with the amine stabilizer. In one embodiment the compositioncomprises, by weight of composition, greater than 60 wt % of NBPT incombination with DCD, the remainder being solvent or a mixture ofsolvents with the amine stabilizer. In one embodiment the compositioncomprises, by weight of composition, greater than 65 wt % of NBPT incombination with DCD, the remainder being solvent or a mixture ofsolvents with the amine stabilizer. In one embodiment the compositioncomprises, by weight of composition, greater than 70 wt % of NBPT incombination with DCD, the remainder being solvent or a mixture ofsolvents with the amine stabilizer. In one embodiment the compositioncomprises, by weight of composition, greater than 75 wt % of NBPT incombination with DCD, the remainder being solvent or a mixture ofsolvents with the amine stabilizer.

In one embodiment the composition comprises, by weight of composition,greater than 30 wt % of DCD and/or NBPT, the remainder being solvent ora mixture of solvents with the amine stabilizer. By way of example, inone embodiment, the fertilizer composition comprises, by weight ofcomposition, 30 wt % of DCD and 70 wt % of a solvent blend of: (i) atleast one dioxolane compound of formula (II.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10.

In one embodiment the composition comprises, by weight of composition,greater than 40 pbw of NBPT (or NBPT in combination with DCD), theremainder being solvent or a mixture of solvents.

In one embodiment the composition comprises, by weight of composition,greater than 35 pbw of NBPT (or NBPT in combination with DCD), theremainder being solvent or a mixture of solvents.

In one embodiment the composition comprises, by weight of composition,greater than 45 pbw of DCD and/or NBPT, the remainder being solvent or amixture of solvents. By way of example, in one embodiment, thefertilizer composition comprises, by weight of composition, 45 wt % ofDCD and 55 wt % of a solvent blend of:

(i) at least one dioxolane compound of formula (II.b) or formula (II.a),wherein R₆ and R₇ are as described above; and(ii) at least one amine stabilizer as described herein.

In one embodiment the composition comprises, by weight of composition,greater than 55 pbw of DCD and/or NBPT, the remainder being solvent or amixture of solvents. By way of example, in one embodiment, thefertilizer composition comprises, by weight of composition, 55 wt % ofDCD and 45 wt % of a solvent blend of:

(i) at least one dioxolane compound of formula (II.b) or formula (II.a),wherein R₆ and R₇ are as described above; and(ii) at least one amine stabilizer as described herein.

EXPERIMENTS

Referring to FIG. 1, Several amines or amides were tested to check ifthey can stabilize NBPT degradation at high temperatures (at greaterthan 45° C.) in NBPT/DMSO formulation. Each sample was prepared with 2wt % of amine stabilizer added. From visual observation, samplesprepared with monoethanolamine showed better physical stability (lessdark appearance), which is believed to be as a result of less formationof dimethyl sulfide (degradation product from solvent).

Referring to FIG. 2, the photograph shows the results from 10 weeksstorage of 2% monoethanolamine in 1:1 NBPT:DMSO at two differenttemperatures, 45° C. and Room Temperature, “RT” (20° C.).

Referring to FIG. 3, it shows a chart of the degradation product, i.e.,dimethyl sulfide (DMS) in parts per million (ppm), measured at varyinghigh temperatures for a period of weeks. The results indicate the liquidfertilizer composition with the amine stabilizer exhibited higherstability over time versus a liquid fertilizer composition without thestabilizer.

What is claimed is:
 1. A high temperature stable liquid agriculturalcomposition comprising at least one urease inhibitor; at least onesolvent selected from: (a) at least one dioxolane compound of formula(I.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10; b) at least one dibasic ester; c) at least one compound of formula(III):R₃OOC-A-CONR₄R₅   (III), wherein R₃ comprises a C₁-C₃₆ alkyl group;wherein R₄ and R₅ individually comprise a C₁-C₃₆ alkyl group, wherein R₄and R₅ can optionally together form a ring; and wherein A is a linear ora branched divalent C₂-C₆ alkyl group; d) at least onealkyldimethylamide; e) at least one alkyl lactate; f) ethyl levulinate;g) at least one alkyoxyalcohol, ether alcohol, amine alcohol, aminoalcohol or alcohol; h) at least one glycerine or glycerine derivative;i) at least one alkylene carbonate; or j) dimethylsulfoxide; and atleast one amine stabilizer selected from monoalkanolamine,dialkanolamine, trialkanolamine, monoethanolamine, diethanolamine ortriethanolamine.
 2. The liquid agricultural composition of claim 1wherein the urease inhibitor is N-(n-butyl)-thiophosphoric triamide(NBPT).
 3. The liquid agricultural composition of claim 1 furthercomprising at least one nitrification inhibitor.
 4. The liquidagricultural composition of claim 1 wherein the amine stabilizer ismonoethanolamine.
 5. The liquid agricultural composition of claim 4wherein the at least one solvent comprises at least one dioxolanecompound of formula (II.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10.
 6. The liquid agricultural composition of claim 1 wherein thecomposition comprises: the at least one urease inhibitor;dimethylsulfoxide; and at least one amine stabilizer selected frommonoalkanolamine, dialkanolamine, trialkanolamine, monoethanolamine,diethanolamine or triethanolamine.
 7. The liquid agriculturalcomposition of claim 1 wherein the at least one a urease inhibitor ispresent in an amount less than about 75 wt %, by total weight ofcomposition.
 8. The liquid agricultural composition of claim 1 whereinthe at least one a urease inhibitor is present in an amount less thanabout 65 wt %, by total weight of composition.
 9. The liquidagricultural composition of claim 1 wherein the at least one a ureaseinhibitor is present in an amount less than about 60 wt %, by totalweight of composition.
 10. The liquid agricultural composition of claim1 wherein the at least one a urease inhibitor is present in an amountless than about 55 wt %, by total weight of composition.
 11. The liquidagricultural composition of claim 1 wherein the at least one a ureaseinhibitor is present in an amount less than about 50 wt %, by totalweight of composition.
 12. The liquid agricultural composition of claim1 wherein the amine stabilizer is present in an amount less than 3 wt %by weight of the liquid fertilizer composition.
 13. The liquidagricultural composition of claim 1 further comprising a secondstabilizer of formula (I.a):

wherein R₁, R₂ and R₃, are each independently chosen from a C₁-C₁₆ alkylgroup, a C₁-C₁₆ alkenyl, group, a C₁-C₁₆ alkoxyalkyl group, a C₇-C₃₀alkylarylalkyl group, a C₇-C₃₀ arylalkyl group, or an aryl group.
 14. Amethod of making a solid or concentrated liquid fertilizer compositioncomprising contacting one or more nitrogenous fertilizer compounds witha liquid inhibitor composition that comprises at least one of an alkylthiophosphoric triamide or dicyandiamide, which is dissolved in a liquidmedium comprising at least one solvent selected from: (a) at least onedioxolane compound of formula (II.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10; b) at least one dibasic ester; c) at least one compound of formula(III):R₃OOC-A-CONR₄R₅   (III), wherein R₃ comprises a C₁-C₃₆ alkyl group;wherein R₄ and R₅ individually comprise a C₁-C₃₆ alkyl group, wherein R₄and R₅ can optionally together form a ring; and wherein A is a linear ora branched divalent C₂-C₆ alkyl group; d) at least onealkyldimethylamide; e) at least one alkyl lactate; f) ethyl levulinate;g) at least one alkyoxyalcohol, ether alcohol, amine alcohol, aminoalcohol or alcohol; h) at least one glycerine or glycerine derivative;i) at least one alkylene carbonate; or j) dimethylsulfoxide; and atleast one amine stabilizer selected from monoalkanolamine,dialkanolamine, trialkanolamine, monoethanolamine, diethanolamine ortriethanolamine.
 15. The method of claim 14 wherein the solventcomprises dimethylsulfoxide.
 16. The method of claim 14 wherein thesolvent comprises: at least one dioxolane compound of formula (II.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10; and dimethylsulfoxide.
 17. A method of stabilizing a liquidfertilizer composition at high temperatures comprising contacting anamine stabilizer with a liquid inhibitor composition that comprises oneor more nitrogenous fertilizer compounds and at least one of adicyandiamide or an alkyl thiophosphoric triamide dissolved in a liquidmedium comprising at least one solvent selected from: (a) at least onedioxolane compound of formula (II.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10; b) at least one dibasic ester; c) at least one compound of formula(III):R₃OOC-A-CONR₄R₅   (III), wherein R₃ comprises a C₁-C₃₆ alkyl group;wherein R₄ and R₅ individually comprise a C₁-C₃₆ alkyl group, wherein R₄and R₅ can optionally together form a ring; and wherein A is a linear ora branched divalent C₂-C₆ alkyl group; d) at least onealkyldimethylamide; e) at least one alkyl lactate; f) ethyl levulinate;g) at least one alkyoxyalcohol, ether alcohol, amine alcohol, aminoalcohol or alcohol; h) at least one glycerine or glycerine derivative;i) at least one alkylene carbonate; or j) dimethylsulfoxide.
 18. Themethod of claim 17 wherein the amine stabilizer is selectedmonoalkanolamine, dialkanolamine, trialkanolamine, monoethanolamine,diethanolamine or triethanolamine.
 19. The method of claim 17 whereinthe amine stabilizer is present in an amount less than 5% by weight ofthe liquid fertilizer composition.
 20. The method of claim 17 whereinthe amine stabilizer is present in an amount less than 4% by weight ofthe liquid fertilizer composition.
 21. The method of claim 17 whereinthe amine stabilizer is present in an amount less than 3% be weight ofthe liquid fertilizer composition.
 22. The method of claim 17 whereinthe amine stabilizer is present in an amount less than 2% be weight ofthe liquid fertilizer composition.
 23. The method of claim 17 whereinthe amine stabilizer is present in an amount less than 1% be weight ofthe liquid fertilizer composition.
 24. A concentrated liquid fertilizercomposition comprising, based on 100 parts by weight of the composition:(a) up to about 99 parts by weight of one or more nitrogenous fertilizercompounds, (b) at least one of an alkyl thiophosphoric triamide or adicyandiamide, (c) at least one solvent; and (d) at least one aminestabilizer.
 25. The concentrated liquid fertilizer composition of claim24 wherein the (c) at least one solvent comprises: (a) at least onedioxolane compound of formula (II.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10; b) at least one dibasic ester; c) at least one compound of formula(III):R₃OOC-A-CONR₄R₅   (III), wherein R₃ comprises a C₁-C₃₆ alkyl group;wherein R₄ and R₅ individually comprise a C₁-C₃₆ alkyl group, wherein R₄and R₅ can optionally together form a ring; and wherein A is a linear ora branched divalent C₂-C₆ alkyl group; d) at least onealkyldimethylamide; e) at least one alkyl lactate; f) ethyl levulinate;g) at least one alkyoxyalcohol, ether alcohol, amine alcohol, aminoalcohol or alcohol; h) at least one glycerine or glycerine derivative;i) at least one alkylene carbonate; j) dimethylsulfoxide; or k) anycombination thereof.
 26. The concentrated liquid fertilizer compositionof claim 24 wherein the (c) at least one solvent comprises: at least onedioxolane compound of formula (II.b):

wherein R₆ and R₇ individually comprises a hydrogen, an alkyl group, analkenyl group, or a phenyl group, wherein n is an integer of from 1 to10; and j) dimethylsulfoxide.
 27. The concentrated liquid fertilizercomposition of claim 24 wherein the (c) at least one solvent comprisesdimethylsulfoxide.